CN100537510C - Chemical method for synthesizing palmitoyl chloride - Google Patents
Chemical method for synthesizing palmitoyl chloride Download PDFInfo
- Publication number
- CN100537510C CN100537510C CNB2006100527956A CN200610052795A CN100537510C CN 100537510 C CN100537510 C CN 100537510C CN B2006100527956 A CNB2006100527956 A CN B2006100527956A CN 200610052795 A CN200610052795 A CN 200610052795A CN 100537510 C CN100537510 C CN 100537510C
- Authority
- CN
- China
- Prior art keywords
- palmitinic acid
- trichloromethyl
- catalyzer
- palmityl chloride
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a method for synthesizing palmitoyl chloride by reacting di (trichloromethyl) carbonate and palmitic acid in an organic solvent in the presence of organic aniline at 50-150 deg.C for 1-10 h. The method uses di(trichloromethyl) carbonate as a substitute for thionyl chloride or phosphorus oxychloride to synthesize palmitoyl chloride, thus has such advantages as advanced reaction route, rational reaction conditions, easy and safe operation, high yield, and few wastes.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of palmityl chloride, particularly use the chemical synthesis process of two (trichloromethyl) carbonic ethers and palmitinic acid prepared in reaction palmityl chloride.
(2) background technology
Palmityl chloride is the important organic intermediate that is used for synthol, phenols cetylate, as producing Syntomycini Palmitas with it.
Before the present invention provided, mostly the chemical synthesis process of palmityl chloride was to prepare with palmitinic acid and phosphorus oxychloride or sulfur oxychloride chloro in the prior art.As making that functional materials 2002,33 (6) proposes with palmitinic acid 18.2g (0.070mol) and sulfur oxychloride 10.4ml (0.035mol) reaction 4h.
Contain a large amount of by product phosphoric acid in the product that phosphorus trichloride method technology obtains, and phosphorus oxychloride is as the seriously corroded of chlorinating agent to equipment, a large amount of phosphorated waste water intractable, pollution problem is serious, and environmental problem is outstanding.Contain a large amount of asphyxiant sulfurous gas (national environmental protection is to one of strict six indexs controlling of atmosphere) in the sulfur oxychloride method process tail gas, difficult treatment, the main at present mixture that adopts alkali to absorb preparation S-WAT and sodium-chlor, but there is big problem in market sale, and, owing to, just can obtain the mixture of S-WAT and sodium-chlor after must concentrating with being the aqueous solution after the alkali absorption, the production process energy consumption is very big, and production cost is higher.The transportation of sulfur oxychloride and use are strictly controlled in addition, to conversion unit sealing requirements height, invest also greatlyyer, and simultaneously former technology also exists problems such as product yield and purity are lower to need to solve.
(3) summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, the chemical synthesis process of the palmityl chloride that production safety is reliable, reaction yield is high, cost is low, the three wastes are little.
The technical solution used in the present invention is as follows:
A kind of chemical synthesis process of palmityl chloride is raw material with palmitinic acid with two (trichloromethyl) carbonic ethers, under the organic amine catalyst action in organic solvent 50～150 ℃ of reaction 1～10h, make described palmityl chloride.Its reaction equation is:
The feed ratio of material is according to described palmitinic acid: two (trichloromethyl) carbonic ether: the amount of substance of organic amine catalyzer is than being 1:0.34～3.0:0.01～1.0, preferred 1:0.34～1.0:0.01～0.20.
Further, described organic amine catalyzer is one of following: triethylamine, pyridine, N-methylpyrrole, 1,3-dimethyl-2-imidazolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-methyl Pyrrolidine, tetramethyl guanidine, tetramethyl-urea, N, the N-dibutyl formamide is preferably 1,3-dimethyl-2-imidazolidone or tetramethyl guanidine.
Organic solvent described in the method is the mixture of following one or more arbitrary proportions: benzene,toluene,xylene, chlorobenzene, dichlorobenzene, normal hexane, hexanaphthene, Di Iso Propyl Ether, dibutyl ether, dioxan, tetrahydrofuran (THF), ethyl acetate, trichloromethane, tetracol phenixin or ethylene dichloride, the mixture of preferred one of following or more than one arbitrary proportions: chlorobenzene, tetrahydrofuran (THF), ethylene dichloride, the consumption of organic solvent are 0.5～5 times of palmitinic acid quality.
Further again, the chemical synthesis process of palmityl chloride, palmitinic acid and two (trichloromethyl) carbonic ethers react under 60～120 ℃ under the organic amine catalyst action, whether the reaction times is 3～8 hours, specifically can according to also have hydrogenchloride to generate and judge reaction end.
Concrete, the chemical synthesis process of palmityl chloride, carry out according to following steps: according to palmitinic acid: two (trichloromethyl) carbonic ether: the amount of substance of organic amine catalyzer feeds intake than for 1:0.34～1.0:0.01～0.20, add organic solvent, measure 0.5～3 times into the palmitinic acid quality, described organic amine catalyzer is a tetramethyl guanidine, described organic solvent is chlorobenzene or tetrahydrofuran (THF), be warming up to 60～120 ℃ of reactions 3～8 hours, normal pressure boils off solvent, and underpressure distillation promptly gets palmityl chloride again.It is 2.3kpa that described underpressure distillation refers to collect vacuum tightness, and temperature is 190～192 ℃ a cut, gets palmityl chloride (C
16H
31C10).
The present invention compared with prior art, its beneficial effect is embodied in:
The present invention with two (trichloromethyl) carbonic ether substitute sulfur oxychloride or phosphorus oxychloride and palmitinic acid under catalyst action in organic solvent the prepared in reaction palmityl chloride, the operational path advanced person, processing condition are reasonable, safety simple to operate, the reaction yield height, production cost is low, and the three wastes are little, has bigger implementary value and economic results in society.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.01, and catalyzer is a tetramethyl guanidine, and organic solvent is a toluene, and its consumption is 2 times of palmitinic acid quality.
In thermometer, reflux condensing tube and churned mechanically 250mL there-necked flask are housed, add palmitinic acid 25.6g (100mmol), two (trichloromethyl) carbonic ether 10.1g (34mmol), toluene 59.5ml and tetramethyl guanidine 0.1g (1mmol).Finish, be warming up to 80 ℃, and at 80～85 ℃ of reaction 7h, after reaction finished, normal pressure boiled off solvent, vacuum tightness is that the cut of 190-192 ℃ of 2.3kpa distillation collection gets palmityl chloride 25.4g, product yield 92.5%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 2
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.7:0.01, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 20.5g (70mmol), catalyzer is 1,3-dimethyl-2-imidazolidone, its consumption is 0.1g (1mmol), and organic solvent is a toluene, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 80～85 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.1g, product yield 91.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 3
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.02, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is a pyridine, its consumption is 0.2g (2mmol), organic solvent is a tetrahydrofuran (THF), and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 60～65 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.1g, product yield 95.0%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 4
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.01, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a pyridine, its consumption is 0.1g (1mmol), organic solvent is a tetrahydrofuran (THF), and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 60～65 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.8g, product yield 90.5%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 5
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.02, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a N-methyl Pyrrolidine, its consumption is 0.2g (2mmol), organic solvent is a chlorobenzene, and its consumption is 3.5 times of palmitinic acid quality.
Temperature of reaction is 85～90 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.7g, product yield 93.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 6
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.05, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a pyridine, its consumption is 0.4g (5mmol), organic solvent is a chlorobenzene, and its consumption is 2.5 times of palmitinic acid quality.
Temperature of reaction is 90-95 ℃, and other is operated with embodiment 1, gets palmityl chloride 23.9g, product yield 87.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 7
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.7:0.1, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 20.5g (70mmol), catalyzer is N, dinethylformamide, its consumption is 0.7g (10mmol), and organic solvent is a chlorobenzene, and its consumption is 0.5 times of palmitinic acid quality.
Temperature of reaction is 100-105 ℃, and other operation gets palmityl chloride 26.2g, product yield 95.5%, purity 98.5% with embodiment 1.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 8
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.0:0.2, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, dinethylformamide, its consumption is 1.8g (20mmol), and organic solvent is a chlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.7g, product yield 90.0%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 9
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.01, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 0.1g (1mmol), and organic solvent is a chlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.8g, product yield 90.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 10
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.02, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 0.2g (2mmol), and organic solvent is a dibutyl ether, and its consumption is 5 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.4g, product yield 89.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 11
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.7:0.03, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 20.5g (70mmol), catalyzer is 1,3-dimethyl-2-imidazolidone, its consumption is 0.3g (3mmol), and organic solvent is a dibutyl ether, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 80～85 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.1g, product yield 91.5%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 12
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.7:0.01, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 20.5g (70mmol), catalyzer is 1,3-dimethyl-2-imidazolidone, its consumption is 0.1g (1mmol), and organic solvent is a dichlorobenzene, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 80～85 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.1g, product yield 88.0%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 13
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.04, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is a pyridine, its consumption is 0.3g (4mmol), organic solvent is a Di Iso Propyl Ether, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 65～68 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.4g, product yield 89.0%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 14
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.06, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a pyridine, its consumption is 0.5g (6mmol), organic solvent is a chlorobenzene, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 90～95 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.4g, product yield 96.5%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 15
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.08, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a N-methyl Pyrrolidine, its consumption is 0.7g (8mmol), organic solvent is a chlorobenzene, and its consumption is 3.5 times of palmitinic acid quality.
Temperature of reaction is 110～115 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.7g, product yield 93.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 16
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.34:0.1, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 10.1g (34mmol), catalyzer is a pyridine, its consumption is 0.8g (10mmol), organic solvent is an ethylene dichloride, and its consumption is 2.5 times of palmitinic acid quality.
Temperature of reaction is 70～75 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.7g, product yield 97.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 17
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:0.7:0.1, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 20.5g (70mmol), catalyzer is N, dinethylformamide, its consumption is 0.7g (10mmol), and organic solvent is a dichlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 115-120 ℃, and other operation gets palmityl chloride 26.2g, product yield 95.5%, purity 98.5% with embodiment 1.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 18
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.0:0.2, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, dinethylformamide, its consumption is 1.5g (20mmol), and organic solvent is a dioxan, and its consumption is 5 times of palmitinic acid quality.
Temperature of reaction is 100-104 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.4g, product yield 96.0%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 19
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.01, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 0.1g (1mmol), and organic solvent is a dimethylbenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.8g, product yield 90.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 20
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1:0.20, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 29.7g (100mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 1.8g (20mmol), and organic solvent is a dibutyl ether, and its consumption is 5 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.4g, product yield 89.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 21
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.5:0.4, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 44.6g (150mmol), catalyzer is a N-methyl Pyrrolidine, its consumption is 3.4g (40mmol), organic solvent is a chlorobenzene, and its consumption is 3.5 times of palmitinic acid quality.
Temperature of reaction is 85～90 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.7g, product yield 93.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment .22
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.5:0.4, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 44.6g (150mmol), catalyzer is a pyridine, its consumption is 3.2g (40mmol), organic solvent is a chlorobenzene, and its consumption is 2.5 times of palmitinic acid quality.
Temperature of reaction is 90-95 ℃, and other is operated with embodiment 1, gets palmityl chloride 23.9g, product yield 87.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 23
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.5:0.4, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 44.6g (150mmol), catalyzer is N, dinethylformamide, its consumption is 2.9g (40mmol), and organic solvent is a chlorobenzene, and its consumption is 0.5 times of palmitinic acid quality.
Temperature of reaction is 100-105 ℃, and other operation gets palmityl chloride 26.2g, product yield 95.5%, purity 98.5% with embodiment 1.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 24
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:1.5:0.4, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 44.6g (150mmol), catalyzer is N, dinethylformamide, its consumption is 2.9g (40mmol), and organic solvent is a chlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.7g, product yield 90.0%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 25
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2:0.6, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 59.4g (200mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 5.2g (60mmol), and organic solvent is a chlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.8g, product yield 90.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 26
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2:0.6, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 59.4g (200mmol), catalyzer is N, the N-N,N-DIMETHYLACETAMIDE, its consumption is 5.2g (60mmol), and organic solvent is a dibutyl ether, and its consumption is 5 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.4g, product yield 89.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 27
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2:0.6, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 59.4g (200mmol), catalyzer is 1,3-dimethyl-2-imidazolidone, its consumption is 6.6g (60mmol), and organic solvent is a dibutyl ether, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 110-115 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.2g, product yield 88.7%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 28
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2.5:0.6, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 74.3g (250mmol), catalyzer is 1,3-dimethyl-2-imidazolidone, its consumption is 6.6g (60mmol), and organic solvent is a dichlorobenzene, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 80～85 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.1g, product yield 88.0%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 29
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2.5:0.8, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 74.3g (250mmol), catalyzer is a pyridine, its consumption is 6.4g (80mmol), organic solvent is a Di Iso Propyl Ether, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 65～68 ℃, and other is operated with embodiment 1, gets palmityl chloride 24.4g, product yield 89.0%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 30
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:2.5:0.8, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 74.3g (250mmol), catalyzer is a pyridine, its consumption is 6.4g (80mmol), organic solvent is a chlorobenzene, and its consumption is 2 times of palmitinic acid quality.
Temperature of reaction is 90～95 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.4g, product yield 96.5%, purity 98.5%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 31
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:3:0.8, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 89.1g (300mmol), catalyzer is a N-methyl Pyrrolidine, its consumption is 6.4g (80mmol), organic solvent is a chlorobenzene, and its consumption is 3.5 times of palmitinic acid quality.
Temperature of reaction is 110～115 ℃, and other is operated with embodiment 1, gets palmityl chloride 25.7g, product yield 93.5%, purity 99.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 32
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:3:1, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 89.1g (300mmol), catalyzer is a pyridine, its consumption is 8.0g (100mmol), organic solvent is an ethylene dichloride, and its consumption is 2.5 times of palmitinic acid quality.
Temperature of reaction is 70～75 ℃, and other is operated with embodiment 1, gets palmityl chloride 26.7g, product yield 97.0%, purity 98.0%.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Embodiment 33
Feed intake amount of substance than palmitinic acid: two (trichloromethyl) carbonic ether: catalyzer is 1:3:1, the palmitinic acid charging capacity is 25.6g (100mmol), two (trichloromethyl) carbonic ether charging capacity is 89.1g (300mmol), catalyzer is N, dinethylformamide, its consumption is 7.3g (100mmol), and organic solvent is a dichlorobenzene, and its consumption is 3 times of palmitinic acid quality.
Temperature of reaction is 115-120 ℃, and other operation gets palmityl chloride 26.2g, product yield 95.5%, purity 98.5% with embodiment 1.
1H?NMR(CDCl
3)δ：2.8(3，2H)，1.6～1.8(m，2H)，1.2～1.4(m，24H)，0.9(3，3H).
Claims (10)
1. the chemical synthesis process of a palmityl chloride is characterized in that described method for being raw material with palmitinic acid with two (trichloromethyl) carbonic ethers, under the organic amine catalyst action in organic solvent 50～150 ℃ of reaction 1～10h, make described palmityl chloride.
2. the chemical synthesis process of palmityl chloride as claimed in claim 1 is characterized in that described palmitinic acid: two (trichloromethyl) carbonic ether: the amount of substance of organic amine catalyzer is than being 1:0.34～3.0:0.01～1.0.
3. the chemical synthesis process of palmityl chloride as claimed in claim 2 is characterized in that described palmitinic acid: two (trichloromethyl) carbonic ether: the amount of substance of organic amine catalyzer is than being 1:0.34～1.0:0.01～0.20.
4. the chemical synthesis process of palmityl chloride as claimed in claim 1, it is characterized in that described organic amine catalyzer is one of following: triethylamine, pyridine, N-methylpyrrole, 1,3-dimethyl-2-imidazolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-methyl Pyrrolidine, tetramethyl guanidine, tetramethyl-urea, N, the N-dibutyl formamide.
5. the chemical synthesis process of palmityl chloride as claimed in claim 4 is characterized in that described organic amine catalyzer is one of following: 1, and 3-dimethyl-2-imidazolidone, tetramethyl guanidine.
6. the chemical synthesis process of palmityl chloride as claimed in claim 1 is characterized in that described organic solvent is the mixture of following one or more arbitrary proportions: benzene,toluene,xylene, chlorobenzene, dichlorobenzene, normal hexane, hexanaphthene, Di Iso Propyl Ether, dibutyl ether, dioxan, tetrahydrofuran (THF), ethyl acetate, trichloromethane, tetracol phenixin or ethylene dichloride.
7. the chemical synthesis process of palmityl chloride as claimed in claim 6 is characterized in that described organic solvent is one of following or the mixture of more than one arbitrary proportions: chlorobenzene, tetrahydrofuran (THF), ethylene dichloride.
8. the chemical synthesis process of palmityl chloride as claimed in claim 7, the consumption that it is characterized in that described organic solvent is 0.5～5 times of palmitinic acid quality.
9. the chemical synthesis process of palmityl chloride as claimed in claim 1 is characterized in that described being reflected under 60～120 ℃ carry out, and the reaction times is 3～8 hours.
10. the chemical synthesis process of palmityl chloride as claimed in claim 1, it is characterized in that described method carries out according to following steps: according to palmitinic acid: two (trichloromethyl) carbonic ether: the amount of substance of catalyzer feeds intake than for 1:0.34～1.0:0.01～0.20, the amount that adds organic solvent is 0.5～3 times of palmitinic acid quality, described catalyzer is a tetramethyl guanidine, described organic solvent is chlorobenzene or tetrahydrofuran (THF), be warming up to 60～120 ℃ of reactions 3～8 hours, normal pressure boils off solvent, and underpressure distillation promptly gets palmityl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100527956A CN100537510C (en) | 2006-08-04 | 2006-08-04 | Chemical method for synthesizing palmitoyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100527956A CN100537510C (en) | 2006-08-04 | 2006-08-04 | Chemical method for synthesizing palmitoyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1915956A CN1915956A (en) | 2007-02-21 |
| CN100537510C true CN100537510C (en) | 2009-09-09 |
Family
ID=37737055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100527956A Expired - Fee Related CN100537510C (en) | 2006-08-04 | 2006-08-04 | Chemical method for synthesizing palmitoyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100537510C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863753B (en) * | 2010-06-17 | 2013-03-06 | 广东广益科技实业有限公司 | Method for preparing palmitoyl chloride |
| CN102863348B (en) * | 2012-09-05 | 2016-08-17 | 长沙普济生物科技有限公司 | A kind of synthetic method of palmitoyl amino acid sodium |
| CN107793312A (en) * | 2016-08-31 | 2018-03-13 | 江苏万隆科技有限公司 | The preparation method of 2,3,4,5 tetrachloro chlorobenzoyl chlorides |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD220597A1 (en) * | 1984-01-04 | 1985-04-03 | Berlin Chemie Veb | PROCESS FOR PREPARING PURE PALMITOYL CHLORIDE |
| CN1535960A (en) * | 2003-04-03 | 2004-10-13 | 浙江工业大学 | Chemical synthesis method of 3-(2-chlorophenyl)-5-methyl-4-isoxazole formyl chloride |
| CN1535959A (en) * | 2003-04-03 | 2004-10-13 | 浙江工业大学 | Chemical synthesis method of 3-phenyl-5-methylisoxazole-4-formyl chloride |
| CN1687000A (en) * | 2005-04-13 | 2005-10-26 | 浙江工业大学 | Method for synthesizing 2,2 dimethyl-3-(2,2-ethylene dichloride) cyclopropane carboxyacyl chloride |
-
2006
- 2006-08-04 CN CNB2006100527956A patent/CN100537510C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD220597A1 (en) * | 1984-01-04 | 1985-04-03 | Berlin Chemie Veb | PROCESS FOR PREPARING PURE PALMITOYL CHLORIDE |
| CN1535960A (en) * | 2003-04-03 | 2004-10-13 | 浙江工业大学 | Chemical synthesis method of 3-(2-chlorophenyl)-5-methyl-4-isoxazole formyl chloride |
| CN1535959A (en) * | 2003-04-03 | 2004-10-13 | 浙江工业大学 | Chemical synthesis method of 3-phenyl-5-methylisoxazole-4-formyl chloride |
| CN1687000A (en) * | 2005-04-13 | 2005-10-26 | 浙江工业大学 | Method for synthesizing 2,2 dimethyl-3-(2,2-ethylene dichloride) cyclopropane carboxyacyl chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1915956A (en) | 2007-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101526030B1 (en) | Inorganic iodide, production method thereof, and production system thereof | |
| CN101372451B (en) | Chemical synthesis method of 2,3,4,5-phenyl tetrafluoride formyl chloride | |
| CN100537510C (en) | Chemical method for synthesizing palmitoyl chloride | |
| CN115894229A (en) | Selective synthesis process of monoethyl adipate | |
| CN101250178A (en) | Chemosynthesis method of 4-chloromethyl-5-methyl-1,3-dioxy heterocyclic pentene-2-ketone | |
| CN112010770A (en) | Novel production method of glycine ethyl ester hydrochloride | |
| CN100500633C (en) | Acetoxy acetyl chloride chemical synthesizing method | |
| JP2012524757A (en) | Method for producing vinyl acetate | |
| CN103450306B (en) | A kind of synthetic method of pregnenolone acetic ester | |
| CN117447427A (en) | Preparation method of furosemide | |
| CN104230703A (en) | Method for synthesizing high-purity benzoyl chloride | |
| CN101891675B (en) | Production method of 6-chloro-2-(trichloromethyl)pyridine | |
| CN109231168B (en) | Method and device for reducing sulfuric acid content in hydrochloric acid and acetic acid by-products in chloroacetic acid production | |
| CN103318958B (en) | Separation and refining method of arsenic trioxide | |
| CN101125815B (en) | Chemical synthesis method for ethyl 6-chloro-6-oxohexanoate | |
| CN111303172B (en) | Method for preparing etodolac methyl ester | |
| CN110563754B (en) | A alcoholysis reaction system for producing chloromethyl triethoxysilane | |
| CN102002009B (en) | Preparation method of 5-methyl isoxazole-4-formyl chloride | |
| CN203816452U (en) | System for treating by-product exhaust generated in chloromethane production | |
| CN104672091B (en) | Containing ethyl acetate and the resource utilization method of the waste material of ethanol in a kind of trifluoroacetic ethyl acetoacetate production process | |
| CN106946772B (en) | A kind of synthetic method of 2,2 '-bipyridyls -4,4 '-methyl formate | |
| US20230074106A1 (en) | Combination preparation process and combination preparation system for zirconia and methylchlorosilane and/or polysilicon | |
| CN101891657A (en) | Manufacturing method of chlorosulfonyl isocyanate | |
| CN105777550B (en) | The method that one kind being continuously synthesizing to 2,4- dinitroanisol | |
| CN101250179B (en) | Chemosynthesis method of 4-bromomethyl-5-methyl-1,3-dioxy heterocyclic pentene-2-ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Taizhou New Oriental Medicine & Chemical Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2010330001098 Denomination of invention: Chemical method for synthesizing palmitoyl chloride Granted publication date: 20090909 License type: Exclusive License Open date: 20070221 Record date: 20100611 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090909 Termination date: 20160804 |